DE339495C - Process for the preparation of resinous condensation products from phenol carboxylic acids and aldehydes - Google Patents

Process for the preparation of resinous condensation products from phenol carboxylic acids and aldehydes

Info

Publication number
DE339495C
DE339495C DE1919339495D DE339495DA DE339495C DE 339495 C DE339495 C DE 339495C DE 1919339495 D DE1919339495 D DE 1919339495D DE 339495D A DE339495D A DE 339495DA DE 339495 C DE339495 C DE 339495C
Authority
DE
Germany
Prior art keywords
aldehydes
preparation
condensation products
carboxylic acids
resinous condensation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
DE1919339495D
Other languages
German (de)
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hoechst AG
Original Assignee
Hoechst AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hoechst AG filed Critical Hoechst AG
Priority claimed from DEF46377D external-priority patent/DE358401C/en
Application granted granted Critical
Publication of DE339495C publication Critical patent/DE339495C/en
Expired legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
    • C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
    • C08G8/18—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with phenols substituted by carboxylic or sulfonic acid groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/28—Chemically modified polycondensates

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Phenolic Resins Or Amino Resins (AREA)

Description

Verfahren zur Darstellung von harzartigen Kondensationsprodukten aus Phenolcarbonsäuren und Aldehyden. Nach den Angaben in Ber.,3i (r898), S. 148 und der Patentschrift 49970, I11. 22, bildet sich bei der Ein-,virkung von Formaldehyd auf Salicylsäure in Gegenwart starker organischer Säuren die Methylendisalicylsäure, ein einheitlicher chemischer Körper. Auch nach den in Ber. 5 (r872), S. 1o96 oben, Ann.263 (189r), S. 285, .amerikanische Patentschrift 7o6354, Archiv der Pharmazie 245 (19o7), S. 42 bis 48, Patentschrift 293866 und britische Patentschrift 4648/igii beschriebenen Verfahren erhält man Proidittkte von wohlcharakterisierter, kriista.lliner Beschaffenheit, welche im Faltre des Verfahrens der britischen Patentschrift 4648/igi i im Gegensatz zu den weiter unten zu beschreibenden nach dehn torliegenden Verfahren zu erhaltenden schwefelhaltig -sind.Process for the preparation of resinous condensation products Phenolic acids and aldehydes. According to the information in Ber., 3i (r898), p. 148 and the patent specification 49970, I11. 22, is formed when formaldehyde acts on salicylic acid in the presence of strong organic acids, methylenedisalicylic acid, a uniform chemical body. Even after the in Ber. 5 (r872), p. 1o96 above, Ann. 263 (189r), p. 285, American patent specification 706354, Archives of Pharmacy 245 (19o7), pp. 42 to 48, patent 293866 and British patent 4648 / igii described method one obtains Proidittkte of well-characterized, kriista.lliner Characteristics which are found in the folder of the method of British patent specification 4648 / igi i in contrast to the method that is to be described below after stretching sulfur-containing to be obtained.

Es wurde nun gefunden, daß die Einwirkung von Formaldehyd oder Formaldehyd abspaltenden Mitteln auf Salicyl'säure, seine Isomeren und Homologen völlig anders verläuft, wenn die Kondensation in Gegenwart von nur geringen Mengen saurer oder basischer Kondensationsmittel oder in ihrer Abwesenheit vorgenommen wird. Man erhält dann unerwarteterweise Körper, welche die Eigenschaften von Harzen besitzen, und zwar haben diese u. a. die .außerordentliche wertvolle Eigenschaft, daß sie nicht nur in Alkohol, Aceton, Paraldehyd usw. löslich sind, sondern auch in wäßrigen Lösungen schwacher Alkalien wie Soda, Borax, Ammoniak, wodurch diese Kunstharze als vollwertiger Ersatz für Naturschellack Verwendung finden können. Beil Anwendung anderer Aldehyde erhält man gleichartige Produkte. Beispiele. I. i 5o Teile o-Oxyla:enzoesäure werden mit einer Mischung von 75 Teilen 3,oprozenti'geni Formalidehyd, Zoo Teilen Wasser 2o. Stunden am Rückflußkühler gekodht. nie ursprünglich klare Lösung scheidet nach einigen Stunden allmählich eine weißliche, durchscheinende Masse aus. Nimmt die Ausscheidung nicht mehr zu und hat diese eine wachsartige Beschaffenheit angenommen, so wird das überschüssige Wasser entfernt und Glas Reaktionsprodukt weiter für sich erhitzt. Erstarrt eine herausgenommene Probe zu einem klaren Glase, so läßt nian erkalten. Das entstandene Produkt ist ein glashelles springhartes Harz von hohem Schmelzpunkt. Es löst sich in Alkohol, Aceton, ferner auch in schwachen AlkaQien, wie wäßriger Sodalösung. Es eignet sich ausgezeichnet fi'tr Lederappretur sowie zu Filzen von Hüten.It has now been found that the action of formaldehyde or formaldehyde Cleaving agents based on salicylic acid, its isomers and homologues are completely different proceeds when the condensation in the presence of only small amounts of acidic or basic condensing agent or in its absence. You get then, unexpectedly, bodies possessing the properties of resins, and although these have a. the extraordinarily valuable property that they are not are only soluble in alcohol, acetone, paraldehyde, etc., but also in aqueous solutions weak alkalis like soda, borax, ammonia, which makes these synthetic resins as full-fledged Substitute for natural shellac can be used. Use of other aldehydes similar products are obtained. Examples. I. i 50 parts of o-oxyla: enzoic acid with a mixture of 75 parts 3, oprozenti'geni formaldehyde, zoo parts water 2o. Coded hours on the reflux condenser. the originally clear solution never separates a whitish, translucent mass gradually develops for a few hours. Take the Excretion no longer closes and has taken on a waxy consistency, so the excess water is removed and the glass of reaction product continues on its own heated. If a sample that has been taken out solidifies to form a clear glass, then nothing can be done to cool off. The resulting product is a crystal-clear, spring-hard resin of high Melting point. It dissolves in alcohol, acetone, and also in weak alcohols, like aqueous soda solution. It is excellent for leather finishing as well for felting hats.

Bei längerer Reaktionsdauer entsteht ein Harz von höherem Schmelzpunkt und größerer Viskosität der alkalischen Lösung. Setzt man dem Ansatz von vornherein ein katalytisch wirkendes Mittel, wie Salzsäure, in geringer Menge zu, so wird die Zeitdauer der Reaktion abgekürzt, iI. 15o Teile eines Gemisches von o- und p-O:Yybenzoesäure werden mit i; Teilen Hexamethylentetramin in 4oo Teilen Weingeist mehrere Stunden am Rückflußkühler gekocht. Die klare, 'schwach gelb gefärbte Lösung wird eingetariäft .ufiad der Rückstand kurze Zeit. auf ;sez,bis@r6o_° erwärmt. Nach Erkalten hinterbeleibt ein iel#u gefärbtes, klar durchsichtiges Harz mit ähnlichen Eigenschaften wie im Beispiel I beschrieben. ` III. z5o Teile Oxytol,uylsäure (OH: CH,: COOH3:4) werden mit 2a Teilen Paraformaldehvd und ; Teilen Amimoni,u!ma!cetat vermischt und kurze Zeit auf 16o bis 17o° erhitzt. Es entsteht ein hellgelbes klares Harz, das sowohl in .@l!kohol wie auch in schwachen Alkalien löslich ist.Longer reaction times result in a resin with a higher melting point and greater viscosity of the alkaline solution. If you take the approach from the start If a catalytically active agent, such as hydrochloric acid, is added in a small amount, the Abbreviated reaction time, iI. 150 parts of a mixture of o- and p-O: yybenzoic acid are with i; Parts of hexamethylenetetramine in 400 parts of alcohol several Boiled for hours on the reflux condenser. The clear, 'pale yellow colored solution becomes einetariäft .ufiad the backlog for a short time. on; sez until @ r6o_ ° warmed up. After cooling down What remains behind is an iel # u colored, clear, transparent resin with similar properties as described in Example I. `III. z5o parts of oxytol, uylic acid (OH: CH ,: COOH3: 4) are with 2a parts Paraformaldehvd and; Share amimoni, u! Ma! Acetate mixed and briefly heated to 16o to 17o °. A light yellow clear resin is formed, the is soluble in alcohol as well as in weak alkalis.

IV. 15o Teile Salicylsäure -werden über ihren_Schmelzpunkt auf etwa r 6o° erhitzt und langsam in kleinen Anteilen 8o Teile Benzaldehyd-Anmm,oniak eingetragen. Es tritt lebhafte Reaktion unter Entwicklung von Ammoniakdämpfen ein. Die Schmelze wird noch kurze Zeit bei 170 bis r8o° gehalten und erkalten gelassen. Sie erstarrt zu einem rötlichgelben, durchsichtigen, in Alkohol und Sodalösung löslichen Harz.IV. 150 parts of salicylic acid are heated above their melting point to about 60 ° and slowly added 80 parts of benzaldehyde ammonia in small proportions. A vigorous reaction occurs with the development of ammonia vapors. The melt is held at 170 to 80 ° for a short time and allowed to cool. It solidifies to a reddish-yellow, transparent resin that is soluble in alcohol and soda solution.

Claims (1)

PATENT-ANSPRUCH.: Verfahren zur Darstellung von harzartigen Kondensationsprodukten aus Phenolcarbonsäuren und Aldehyden, dadurch gekennzeichnet, daß nnan arcmat,i!s:che Oxycarbonsäuren mit Aldehyd oder Aldehyd abspaltenden Mitteln, in Abwesenheit oder Anwesenheit geringer, Mengen saurer oder basischer Kondensationsmittel, in Gegenwart oder Abwesenheit von Lösungsmitteln, erhitzt.PATENT CLAIM: Process for the preparation of resinous condensation products from phenol carboxylic acids and aldehydes, characterized in that nnan arcmat, i! s: che Oxycarboxylic acids with aldehyde or aldehyde-releasing agents, in the absence of or Presence of small amounts of acidic or basic condensing agents in the presence or absence of solvents, heated.
DE1919339495D 1919-11-15 1919-11-15 Process for the preparation of resinous condensation products from phenol carboxylic acids and aldehydes Expired DE339495C (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE339495T 1919-11-15
DEF46377D DE358401C (en) 1919-11-15 1920-03-04 Process for the preparation of resinous condensation products from phenol carboxylic acids and aldehydes
DEF46508D DE362382C (en) 1919-11-15 1920-03-29 Process for the preparation of resinous condensation products from phenols and aldehyde or ketone derivatives

Publications (1)

Publication Number Publication Date
DE339495C true DE339495C (en) 1922-04-07

Family

ID=41682713

Family Applications (1)

Application Number Title Priority Date Filing Date
DE1919339495D Expired DE339495C (en) 1919-11-15 1919-11-15 Process for the preparation of resinous condensation products from phenol carboxylic acids and aldehydes

Country Status (1)

Country Link
DE (1) DE339495C (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1114965B (en) * 1958-08-20 1961-10-12 Bayer Ag Priming metals

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1114965B (en) * 1958-08-20 1961-10-12 Bayer Ag Priming metals

Similar Documents

Publication Publication Date Title
DE576177C (en) Process for the production of resinous products from phenol condensation products and polyhydric alcohols
DE749553C (en) Process for the production of cation-exchanging synthetic resins
DE339495C (en) Process for the preparation of resinous condensation products from phenol carboxylic acids and aldehydes
DE674984C (en) Process for the preparation of reaction products of styrene
DE474561C (en) Process for the preparation of ester-like derivatives of the condensation products of phenols and carbonyl compounds
DE364042C (en) Process for the preparation of condensation products from ethylene glycol monoaryl ethers
DE564525C (en) Process for the production of resin solutions
DE673962C (en) Process for the manufacture of drying ointments
DE942595C (en) Process for the production of resinous co-condensation products
DE495790C (en) Process for the production of urea-formaldehyde condensation products
DE829926C (en) Process for the production of lightfast modified phenolic resins
DE674968C (en) Process for the preparation of phenolic aralkylamino alcohols
DE872946C (en) Process for the production of condensation products
DE711687C (en) Process for the production of resinous substances
DE569486C (en) Process for the preparation of phenol-formaldehyde condensation products
DE193136C (en)
DE529323C (en) Process for the production of a viscous condensation product from phenol and formaldehyde
DE434830C (en) Process for the preparation of paraformaldehyde-free solutions of polymeric formaldehyde in monohydric or polyhydric alcohols
DE712701C (en) Process for the production of phenol aldehyde resins suitable as paint base
DE371147C (en) Process for the production of resinous condensation products from aryloxyacetic acids and formaldehyde
DE344033C (en) Process for the preparation of water-soluble condensation products from aliphatic aldehydes and di- or polyoxybenzenes
AT124516B (en) Process for the production of phenol-formaldehyde condensation products.
AT156166B (en) Process for the production of resinous condensation products.
DE474787C (en) Process for refining recent natural resins
DE905316C (en) Process for the production of catechinaldehyde synthetic resins